Hierarchical assembly of discrete copper(II) metallo-structures from pre-assembled dinuclear (bis-β-diketonato)metallocycles and flexible difunctional co-ligands

Clegg, Jack K., Li, Feng, Jolliffe, Katrina A., Lindoy, Leonard F., Meehan, George V., Parsons, Simon, Tasker, Peter A., and White, Fraser J. (2013) Hierarchical assembly of discrete copper(II) metallo-structures from pre-assembled dinuclear (bis-β-diketonato)metallocycles and flexible difunctional co-ligands. Dalton Transactions, 42 (39). pp. 14315-14323.

[img] PDF (Published Version) - Published Version
Restricted to Repository staff only

View at Publisher Website: http://dx.doi.org/10.1039/c3dt51531a


The sequential interaction of preformed [Cu2(L111)2(THF)2] (where H2L111 is 1,1-(1,3-phenylene)-bis(4,4-dimethylpentane-1,3-dione incorporating a 1,3-phenylene linker between its two β-diketone domains) and [Cu2(L444)2]·2H2O (where H2L444 is 1,1-(4,4'-oxybiphenylene)-bis(4,4-dimethylpentane-1,3-dione) incorporating a flexible oxybiphenylene linkage between the two β-diketone groups) with the potentially difunctional aliphatic non-planar co-ligands, N-methylpiperazine (mpip), N,N'-dimethylpiperazine (dmpip) and 1,4-thiomorpholine (thiomorph) is reported. A series of extended molecular assemblies exhibiting a range of di- and tetranuclear assemblies were obtained and their X-ray structures determined. Dinuclear [Cu2(L111)2(mpip)2]·2mpip incorporates two 5-coordinate, square pyramidal metal centres as does tetranuclear [{Cu2(L111)2}2(dmpip)2]·2dmpip. In contrast, dinuclear [Cu2(L111)2(dmpip)4]·dmpip and [{Cu2(L111)2}2(thiomorph)4]·3thiomorph each contain two 5-coordinate and two 6-coordinate centres. Each of [Cu2(L444)2(THF)2]·2THF and Cu2(L444)2(mpip)2]·H2O incorporate only 5-coordinate metal centres, with the latter complex forming a one-dimensional hydrogen bonded ribbon-like structure directed along the crystallographic a-axis. In keeping with the documented tendency for the smallest, least strained assembly to form in supramolecular self-assembly processes, the incorporation of the flexible "oxy" linkage between the 4,4'-linked phenylene rings of H2L333 results in generation of a dinuclear [Cu2L22] species rather than a trinuclear (triangular) [Cu3L333] species of the type formed by the more rigid bis-β-diketonato ligand analogue in which the biphenylene rings separating the β-diketone domains are directly coupled in their 4,4' positions.

Item ID: 30205
Item Type: Article (Research - C1)
ISSN: 1477-9234
Date Deposited: 13 Nov 2013 05:36
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
Downloads: Total: 4
More Statistics

Actions (Repository Staff Only)

Item Control Page Item Control Page